CN101613420B - Preparation method of 2-hydroxypropyl trimethyl ammonium chloride chitosan - Google Patents
Preparation method of 2-hydroxypropyl trimethyl ammonium chloride chitosan Download PDFInfo
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- CN101613420B CN101613420B CN2009101443932A CN200910144393A CN101613420B CN 101613420 B CN101613420 B CN 101613420B CN 2009101443932 A CN2009101443932 A CN 2009101443932A CN 200910144393 A CN200910144393 A CN 200910144393A CN 101613420 B CN101613420 B CN 101613420B
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- RUUHDEGJEGHQKL-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)C RUUHDEGJEGHQKL-UHFFFAOYSA-M 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000007670 refining Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000006196 deacetylation Effects 0.000 claims description 20
- 238000003381 deacetylation reaction Methods 0.000 claims description 20
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 8
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- 238000001914 filtration Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000003828 vacuum filtration Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
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- 238000007654 immersion Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
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- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 239000012620 biological material Substances 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
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- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 3
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- 241000628997 Flos Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- HMHFERXOZSZRML-UHFFFAOYSA-M trimethyl-(3-methyloxiran-2-yl)azanium;chloride Chemical compound [Cl-].CC1OC1[N+](C)(C)C HMHFERXOZSZRML-UHFFFAOYSA-M 0.000 description 3
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Abstract
The invention provides a preparation method of 2-hydroxypropyl trimethyl ammonium chloride chitosan, belonging to the technical field of novel biological materials. The method solves the problems that the existing preparation method of the chitosan quaternary ammonium salt has high cost, complicated steps and low yield, and the performance of the obtained chitosan quaternary ammonium salt product is difficult to meet the requirements of people. The preparation method of the 2-hydroxypropyl trimethyl ammonium chloride chitosan comprises the following steps: A. soaking chitosan; B. complex phase reaction; C. and (5) refining. The preparation method of the 2-hydroxypropyl trimethyl ammonium chloride chitosan has the advantages of less solvent consumption and high raw material stability. The 2-hydroxypropyl trimethyl ammonium chloride chitosan prepared by the preparation method has high yield and purity, and has good quality indexes such as moisture retention, hygroscopicity and antibacterial property.
Description
Technical field
The present invention relates to a kind of preparation method of chitosan quaternary ammonium salt, particularly a kind of preparation method of 2-HACC; Belong to the novel biomaterial technical field.
Background technology
Chitosan quaternary ammonium salt is one type of important chitosan derivatives; Advantages such as chitosan excellent biological compatibility, degradability have been inherited; But also have many new performances;, biocidal property moist like good water-solubility, guarantor's (suction), flocculence and stronger electrostatic adhesion property, in biological medicine, weaving, fields such as material for water treatment and environmental protection have obtained widespread use.Its mixture is existing lot of documents report aspect pharmaceutical excipients such as gene, medicine carrying, antibiotic wound material, anticoagulant material, breaks through having great novelty, and its market application foreground is wide.Therefore, the preparation technology of research chitosan quaternary ammonium salt is significant.
Existing chitosan quaternary ammonium salt generally can make through N-alkylation, ester-interchange method and epoxy derivative open loop method; Wherein adopt the N-alkylation to prepare the chitosan quaternary ammonium salt low in raw material cost and be easy to get, but used methyl iodide boiling point is low, if temperature of reaction is too high; Methyl iodide volatile and the waste reagent; Thereby be difficult to control reacting material ratio, solvent N-N-methyl-2-2-pyrrolidone N-cost used in the reaction process is higher, and toxicity is big; On the other hand, this reaction needed is the iodate N-TMC salt of preparation poor stability earlier, is converted into chlorination N-TMC salt again, and reactions step is more, influences productive rate.Ester-interchange method is that triethylamine is added drop-wise in the quantitative ethyl chloroacetate; Under suitable temperature, react the regular hour; Make quaternized ethyl chloroacetate, again chitosan and quaternized ethyl chloroacetate are carried out transesterification reaction, this method side reaction is few; But need the quaternized ethyl chloroacetate of synthetic mesophase product, step is more loaded down with trivial details.
Adopting the used graft modification agent of epoxy derivative open loop method mainly is the epoxypropyl trimethylammonium chloride ammonium, and it is to accomplish ring-opening reaction through the interatomic effect of active H in epoxide group in the epoxypropyl trimethylammonium chloride ammonium (GTMAC) and the chitosan (CTS).But because epoxypropyl trimethylammonium chloride ammonium (GTMAC) easy hydrolysis under neutrality or alkaline condition forms 2; 3-dihydroxypropyl trimethyl ammonium chloride and lose with chitosan (CTS) key bonded ability; And intermolecular polymerization also takes place and reduces the grafting efficiency to chitosan (CTS) in epoxypropyl trimethylammonium chloride ammonium (GTMAC) easily in alcohol, water; Chitosan (CTS) chemical modification cost is increased, and the chitosan quaternary ammonium performance of products that obtains is difficult to satisfy people's requirement.
Summary of the invention
The present invention is directed to the defective that prior art exists, provide a kind of reactions step few, technical process is simple, the preparation method of the 2-HACC that the finished product purity and yield are higher.
Above-mentioned technical purpose of the present invention is able to implement through following technical scheme: a kind of preparation method of 2-HACC, and this method may further comprise the steps:
The immersion treatment of A, chitosan: the chitosan that will pass through deacetylated processing is dissolved in fully in the acid solution and soaked 5-10 hour, and vacuum filtration stirs after the dilution filtrating then, adds solvent then and separates out chitosan;
B, heterogeneous reaction: in above-mentioned chitosan solvent of separating out, drip 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and carry out heterogeneous reaction; Temperature of reaction is 75 ℃～90 ℃; Reaction times is 8-15 hour; Reaction finishes after-filtration, and vacuum distilling adds solvent then and separates out 2-HACC bullion; With carrying out vacuum-drying behind the immersion of 2-HACC bullion, the suction filtration;
C, refining: the 2-HACC bullion after the above-mentioned vacuum-drying is water-soluble, filter, filtrating post precipitation in solvent, whiz obtain refining 2-HACC.
The present invention utilizes the principle of heterogeneous reaction, and chitosan is dissolved in the acid; Add solvent then and chitosan is separated out (white floss).Drip of the surface reaction of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, thereby strengthened reaction contact area at chitosan; The chitosan of separating out (white floss) disappears, and the sign reaction finishes.Because this reaction is heterogeneous reaction, so be that the product that the medium reaction obtains can be transferred in the water with the solvent, products therefrom is soluble in water, according to the chemical reaction equilibrium principle, reaction can be carried out preferably to the right, thereby improves the product yield.
And existing 2,3-epoxypropyl trimethylammonium chloride ammonium is to accomplish reaction through the interatomic effect of active H in epoxide group and the chitosan.But because 2; The easy hydrolysis under neutrality or alkaline condition of 3-epoxypropyl trimethylammonium chloride ammonium forms 2; 3-dihydroxypropyl trimethyl ammonium chloride and losing and chitosan key bonded ability, and 2, intermolecular polymerization also takes place and reduces the grafting efficiency to chitosan in 3-epoxypropyl trimethylammonium chloride ammonium easily in alcohol, water; Chitosan chemical modification cost is increased, and the chitosan quaternary ammonium performance of products that obtains is difficult to satisfy people's requirement.The 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride that the present invention adopts is the midbody of synthesizing epoxy oxypropyl trimethyl ammonium chloride; Under strong alkaline condition, can be converted into the epoxypropyl trimethylammonium chloride ammonium; Adopt 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride to solve 2 as the active cation etherifying agent at the cation modifying of chitosan, the deficiency that the modification cost that exists during 3-epoxypropyl trimethylammonium chloride ammonium modified chitosan is high, grafting efficiency is low.And cheap being easy to get of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride raw material is fit to large-scale industrial production.
In the preparation method of above-mentioned 2-HACC; The detailed process of the deacetylated processing of chitosan described in the steps A is: chitosan is joined in the strong base solution; In temperature is 110 ℃～120 ℃; Pressure is stirring reaction 5～15 hours under 0.2Mpa～0.4Mpa condition, obtains deacetylation and be 85%～95% chitosan.The present invention can also adopt the chitosan or the chitin of low acetyl degree to reach 85%～95% chitosan as feedstock production acetyl degree.As preferably, the acetyl degree of described chitosan is 90%～95%.Used strong base solution is that massfraction is 15%～25% NaOH or KOH solution, and the present invention adopts deacetylation to reach the 85%-95% chitosan to help improving product gas purity; Because reaction is on the amino of chitosan, to carry out, the too low meeting of its deacetylation causes reaction products obtained therefrom purity very low, and the too high purity increase rate to the finished product of deacetylation is little, but cost is too high.
In the preparation method of above-mentioned 2-HACC, the acid solution described in the steps A is that massfraction is 1%～2% acetic acid, and massfraction is 1%～10% phosphoric acid, and massfraction is a kind of in 0.5%～1% the hydrochloric acid.As preferably, described acid solution is that massfraction is 1%～2% acetic acid.Further preferred, described acid solution is that massfraction is 1% acetic acid.
In the preparation method of above-mentioned 2-HACC, the solvent described in the steps A is a kind of in Virahol, methyl alcohol, the acetone.As preferably, described solvent is a Virahol.Drip Virahol when separating out chitosan, chitosan is separated out is shaped as white floss, thereby is the heterogeneous reaction augmenting response area among the step B.Virahol can also be as protective material, and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride adds and mainly on amino, to react, and on the alcoholic extract hydroxyl group of No. 6 positions, reacting seldom also arranged, and Virahol can make the alcoholic extract hydroxyl group steric effect of No. 6 positions of chitosan become bigger.
In the preparation method of above-mentioned 2-HACC, the mass ratio of chitosan described in the step B and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is 1: 3～7; Whenever dripped a 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride at a distance from 2 hours, divide to drip off for 3 times, the dropping time was controlled at 20～30 minutes at every turn.As preferably, the mass ratio of described chitosan and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is 1: 4～6.
In the preparation method of above-mentioned 2-HACC, the temperature of the heterogeneous reaction described in the step B is for being 80 ℃～85 ℃, and the reaction times is 10-14 hour.
In the preparation method of above-mentioned 2-HACC, the solvent of separating out 2-HACC bullion among the step B is a kind of in Virahol, methyl alcohol, acetone and the absolute ethyl alcohol.As preferably, the solvent of separating out 2-HACC bullion among the step B is a kind of in Virahol, the absolute ethyl alcohol.Because 2-HACC bullion is water-soluble, and Virahol and absolute ethyl alcohol can be used as water-retaining agent, thereby the maximized water-soluble final yield that influences of bullion that reduced.
In the preparation method of above-mentioned 2-HACC, vacuum drying temperature is 50 ℃～70 ℃ among the step B.
In the preparation method of above-mentioned 2-HACC, adopt the 3G sand core funnel to filter among the step C.Owing to insolubles and impurity are arranged in the 2-HACC bullion, water-soluble after, can utilize the 3G sand core funnel to remove by filter these impurity.
In the preparation method of above-mentioned 2-HACC, the solvent described in the step C is a kind of in Virahol, methyl alcohol, acetone and the absolute ethyl alcohol.As preferably, the solvent described in the step C is a kind of in Virahol, the absolute ethyl alcohol.Virahol and absolute ethyl alcohol can be used as water-retaining agent, and it is water-soluble and reduce yield to reduce product, and Virahol and absolute ethyl alcohol are volatile in addition, are convenient to drying; And acetone has part residual after separating out, and also need use absolute ethanol washing, has increased cost; Methyl alcohol is toxic.
The present invention feeds intake mass ratio, temperature of reaction, reaction times, deacetylating degree of chitosan as experimental factor with material, checks each factor to the productive rate of aqueous solution chitosan quaternary ammonium salt and the influence of quality, confirms each optimum addition.
Carry out comprehensive grading according to the color and luster state of water-soluble chitosan quaternary ammonium salt, solvability, PH stability, water absorbability, moisture retention, film-forming properties, bacterinertness etc.Sample offers 10 experienced specialties at random and evaluates personnel, and product is given a mark respectively, makes even to be divided into total sensory evaluation scores.The sensory evaluation scores standard is seen table 1.
Table 1 sensory evaluation scores standard
Chitosan is better in 1% acetum solvability; The optimal dissolution degree of chitosan is about 3%; 3-chlorine 2-hydroxypropyl-trimethyl ammonium chloride is chosen in this experiment: chitosan is respectively and reacted in 3: 1,4: 1,5: 1,6: 1; Detect after oven dry is pulverized, the yield and the quality index of the sample that obtains are marked its result such as table 2.
The influence of mass ratio that feed intake of table 2 material to water-soluble chitosan quaternary ammonium salt yield and quality
From table 2, can find out; Along with the feed intake difference of mass ratio of material, the yield and the quality of sample also change thereupon, when 3-chlorine 2-hydroxypropyl-trimethyl ammonium chloride: when chitosan is 1: 5; Product each item sensory evaluation scores is the highest, obtainable sample yield and best in quality.
Can the height of temperature directly have influence on 3-chlorine 2-hydroxypropyl-trimethyl ammonium chloride and receive on the amino of chitosan; This experiment is chosen under 65 ℃, 75 ℃, 80 ℃, 85 ℃ the temperature condition; Under the material proportion of the best, react; Detect after oven dry is pulverized, the yield and the quality index of the sample that obtains are marked its result such as table 3.
Table 3 temperature of reaction is to the influence of water-soluble chitosan quaternary ammonium salt yield and quality
Can find out that from table 3 when temperature of reaction was 80 ℃, product each item sensory evaluation scores was the highest, obtainable sample yield and best in quality.
The length in reaction times has very big influence to the yield of chitosan quaternary ammonium salt, and the time is too short, and reaction not exclusively promptly has chitosan also to have little time to participate in reaction, and the soluble quaternary ammonium of making is insoluble to too much; Time is long, though react completely, side reaction possibly take place, and also is very to calculate from the angle of energy consumption.It is the reaction times of chitosan and 3-chlorine 2-hydroxypropyl-trimethyl ammonium chloride that 8h, 9h, 10h, 11h, 12h are chosen in this experiment; Under best proportioning and optimum temps, react; Detect after oven dry is pulverized the yield and the quality index of the sample that obtains are marked its result such as table 4.
Table 4 reaction times is to the influence of water-soluble chitosan quaternary ammonium salt yield and quality
Can find out that from table 4 reaction times, product each item sensory evaluation scores was the highest when 10h, obtainable sample yield and best in quality.
The height of deacetylation directly has influence on the amino of 3-chlorine 2-hydroxypropyl-trimethyl ammonium chloride street chitosan; It is that 85%, 90%, 95%, 98% chitosan carries out reacting under best proportioning and the condition that deacetylation is chosen in this experiment; Detect after oven dry is pulverized the yield and the quality index of the sample that obtains are marked its result such as table 5.
The deacetylation of table 5 chitosan is to the influence of water-soluble chitosan quaternary ammonium salt yield and quality
Can find out that from table 5 deacetylating degree of chitosan changes, the yield and the quality of sample also change thereupon, and when deacetylating degree of chitosan was 98%, product each item sensory evaluation scores was the highest, obtainable sample yield and best in quality.
Chemical equation of the present invention is as follows:
In sum, the present invention compared with prior art has the following advantages:
1, utilize the 2-HACC productive rate height and the purity of preparing method's preparation of the present invention higher, productive rate and purity can both get at more than 90%.
2, preparing method's solvent load of 2-HACC of the present invention is few, and the solvent of adding just plays the effect of medium, and purpose is in acetum, slowly to separate out chitosan.
3, the raw material 3-chlorine 2-hydroxypropyl-trimethyl ammonium chloride character used of the preparation method of 2-HACC of the present invention is more stable, side reaction can not take place in water.
4, utilize the quality index such as 2-HACC moisture retention, water absorbability, bacterinertness of preparation method of the present invention preparation better.
Description of drawings
Fig. 1 is the preparing method's of this 2-HACC a process flow sheet.
Embodiment
Through specific embodiment and combine accompanying drawing, do further bright specifically below to technical scheme of the present invention; But the present invention is not limited to these embodiment.
Embodiment 1
It is in 20% the NaOH solution that chitosan is joined massfraction, is 110 ℃ in temperature, and pressure is stirring reaction 15 hours under the 0.2Mpa condition, the supernatant liquid that inclines, and deionized water is washed till neutrality.Obtain deacetylation and be 90% chitosan.
With the 5g deacetylation is that to be dissolved in massfraction be in 1% the acetum for 90% chitosan; In temperature is to soak dissolving fully in 5 hours, vacuum filtration, elimination insolubles in 60 ℃ of water-baths; Adding deionized water 40ml dilution filtrating is also poured in the there-necked flask; Stirred 30 minutes, and added the 80ml Virahol then and separate out chitosan, divide three addings 20g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride wiring solution-forming; Every added once at a distance from 2 hours, titration time is controlled at half hour and carries out heterogeneous reaction at every turn.Temperature of reaction is 80 ℃, and the reaction times is 10 hours, and reaction finishes back solution becomes clarification; With liquid filtering elimination insolubles, under vacuum condition, distill out half water after, add absolute ethyl alcohol and separate out 2-HACC bullion; Soak half hour; Suction filtration, 65 ℃ of following vacuum-dryings, 2-HACC bullion color is faint yellow.Dried 2-HACC bullion is water-soluble; The 3G sand core funnel filters; Filtrating is precipitated in its 5 times of absolute ethyl alcohol volumes and is obtained light yellow precipitate; Whiz can be made with extra care 2-HACC quaternary ammonium salt, and yield is 90.5%, and purity is 93%.Its process flow sheet is as shown in Figure 1.
Embodiment 2
It is in 20% the NaOH solution that chitosan is joined massfraction, is 120 ℃ in temperature, and pressure is stirring reaction 10 hours under the 0.4Mpa condition, the supernatant liquid that inclines, and deionized water is washed till neutrality.Obtain deacetylation and be 95% chitosan.
With the 10g deacetylation is that to be dissolved in massfraction be in 1% the acetum for 95% chitosan; In temperature is to soak dissolving fully in 8 hours, vacuum filtration, elimination insolubles in 60 ℃ of water-baths; Adding deionized water 40ml dilution filtrating is also poured in the there-necked flask; Stirred 30 minutes, and added the 80ml Virahol then and separate out chitosan, divide three addings 50g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride wiring solution-forming; Every added once at a distance from 2 hours, titration time is controlled at half hour and carries out heterogeneous reaction at every turn.Temperature of reaction is 80 ℃, and the reaction times is 12 hours, and reaction finishes back solution becomes clarification; With liquid filtering elimination insolubles, under vacuum condition, distill out half water after, add absolute ethyl alcohol and separate out 2-HACC bullion; Soak half hour; Suction filtration, 65 ℃ of following vacuum-dryings, 2-HACC bullion color is faint yellow.Dried 2-HACC bullion is water-soluble; The 3G sand core funnel filters; Filtrating is precipitated in its 5 times of absolute ethyl alcohol volumes and is obtained light yellow precipitate; Whiz can be made with extra care 2-HACC quaternary ammonium salt, and yield is 91.0%, and purity is 92.5%.
Embodiment 3
It is in 20% the NaOH solution that chitosan is joined massfraction, is 115 ℃ in temperature, and pressure is stirring reaction 6 hours under the 0.3Mpa condition, the supernatant liquid that inclines, and deionized water is washed till neutrality.Obtain deacetylation and be 95% chitosan.
With the 12g deacetylation is that to be dissolved in massfraction be in 1% the acetum for 95% chitosan; In temperature is to soak dissolving fully in 10 hours, vacuum filtration, elimination insolubles in 60 ℃ of water-baths; Adding deionized water 40ml dilution filtrating is also poured in the there-necked flask; Stirred 30 minutes, and added the 80ml Virahol then and separate out chitosan, divide three addings 72g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride wiring solution-forming; Every added once at a distance from 2 hours, titration time is controlled at half hour and carries out heterogeneous reaction at every turn.Temperature of reaction is 80 ℃, and the reaction times is 14 hours, and reaction finishes back solution becomes clarification; With liquid filtering elimination insolubles, under vacuum condition, distill out half water after, add absolute ethyl alcohol and separate out 2-HACC bullion; Soak half hour; Suction filtration, 65 ℃ of following vacuum-dryings, 2-HACC bullion color is faint yellow.Dried 2-HACC bullion is water-soluble; The 3G sand core funnel filters; Filtrating is precipitated in its 5 times of absolute ethyl alcohol volumes and is obtained light yellow precipitate; Whiz can be made with extra care 2-HACC quaternary ammonium salt, and yield is 92.0%, and purity is 90.5%.
Embodiment 4
It is in 20% the NaOH solution that chitosan is joined massfraction, is 110 ℃ in temperature, and pressure is stirring reaction 10 hours under the 0.3Mpa condition, the supernatant liquid that inclines, and deionized water is washed till neutrality.Obtain deacetylation and be 90% chitosan.
With the 10g deacetylation is that to be dissolved in massfraction be in 2% the acetum for 90% chitosan; In temperature is to soak dissolving fully in 8 hours, vacuum filtration, elimination insolubles in 60 ℃ of water-baths; Adding deionized water 40ml dilution filtrating is also poured in the there-necked flask; Stirred 30 minutes, and added 80ml methyl alcohol then and separate out chitosan, divide three addings 50g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride wiring solution-forming; Every added once at a distance from 2 hours, titration time is controlled at half hour and carries out heterogeneous reaction at every turn.Temperature of reaction is 85 ℃, and the reaction times is 10 hours, and reaction finishes back solution becomes clarification; With liquid filtering elimination insolubles, under vacuum condition, distill out half water after, add Virahol and separate out 2-HACC bullion; Soak half hour; Suction filtration, 60 ℃ of following vacuum-dryings, 2-HACC bullion color is faint yellow.Dried 2-HACC bullion is water-soluble; The 3G sand core funnel filters; Filtrating is precipitated in its 5 times of Virahol volumes and is obtained light yellow precipitate; Whiz can be made with extra care 2-HACC quaternary ammonium salt, and yield is 91.0%, and purity is 92.0%.
Embodiment 5
It is in 20% the NaOH solution that chitosan is joined massfraction, is 120 ℃ in temperature, and pressure is stirring reaction 10 hours under the 0.3Mpa condition, the supernatant liquid that inclines, and deionized water is washed till neutrality.Obtain deacetylation and be 95% chitosan.
With the 10g deacetylation is that to be dissolved in massfraction be in 2% the phosphoric acid solution for 95% chitosan; In temperature is to soak dissolving fully in 6 hours, vacuum filtration, elimination insolubles in 60 ℃ of water-baths; Adding deionized water 40ml dilution filtrating is also poured in the there-necked flask; Stirred 30 minutes, and added 80ml acetone then and separate out chitosan, divide three addings 50g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride wiring solution-forming; Every added once at a distance from 2 hours, titration time is controlled at half hour and carries out heterogeneous reaction at every turn.Temperature of reaction is 88 ℃, and the reaction times is 10 hours, and reaction finishes back solution becomes clarification; With liquid filtering elimination insolubles, under vacuum condition, distill out half water after, add absolute ethyl alcohol and separate out 2-HACC bullion; Soak half hour; Suction filtration, 55 ℃ of following vacuum-dryings, 2-HACC bullion color is faint yellow.Dried 2-HACC bullion is water-soluble; The 3G sand core funnel filters; Filtrating is precipitated in its 5 times different absolute ethyl alcohol volumes and is obtained light yellow precipitate; Whiz can be made with extra care 2-HACC quaternary ammonium salt, and yield is 90.5%, and purity is 91.5%.
Embodiment 6
It is in 20% the NaOH solution that chitosan is joined massfraction, is 110 ℃ in temperature, and pressure is stirring reaction 5 hours under the 0.2Mpa condition, the supernatant liquid that inclines, and deionized water is washed till neutrality.Obtain deacetylation and be 85% chitosan.
With the 10g deacetylation is that to be dissolved in massfraction be in 0.5% the hydrochloric acid soln for 85% chitosan; In temperature is to soak dissolving fully in 10 hours, vacuum filtration, elimination insolubles in 60 ℃ of water-baths; Adding deionized water 40ml dilution filtrating is also poured in the there-necked flask; Stirred 30 minutes, and added the 80ml Virahol then and separate out chitosan, divide three addings 50g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride wiring solution-forming; Every added once at a distance from 2 hours, titration time is controlled at half hour and carries out heterogeneous reaction at every turn.Temperature of reaction is 80 ℃, and the reaction times is 15 hours, and reaction finishes back solution becomes clarification; With liquid filtering elimination insolubles, under vacuum condition, distill out half water after, add methyl alcohol and separate out 2-HACC bullion; Soak half hour; Suction filtration, 65 ℃ of following vacuum-dryings, 2-HACC bullion color is faint yellow.Dried 2-HACC bullion is water-soluble; The 3G sand core funnel filters; Filtrating is precipitated in its 5 times of methyl alcohol volumes and is obtained light yellow precipitate; Whiz can be made with extra care 2-HACC quaternary ammonium salt, and yield is 92.5%, and purity is 90.0%.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.Person of ordinary skill in the field of the present invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some specific embodiments as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (9)
1. the preparation method of a 2-HACC, this method may further comprise the steps:
The immersion treatment of A, chitosan: the chitosan that will pass through deacetylated processing is dissolved in fully in the acid solution and soaked 5-10 hour; Vacuum filtration then; Stir dilution filtrating back; Add solvent then and separate out chitosan, described acid solution is that massfraction is that 1%～2% acetic acid, massfraction are that 1%～10% phosphoric acid, massfraction are a kind of in 0.5%～1% the hydrochloric acid;
B, heterogeneous reaction: in above-mentioned chitosan solvent of separating out, drip 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and carry out heterogeneous reaction; Temperature of reaction is 75 ℃～90 ℃; Reaction times is 8-15 hour; Reaction finishes after-filtration, and vacuum distilling adds solvent then and separates out 2-HACC bullion; With carrying out vacuum-drying behind the immersion of 2-HACC bullion, the suction filtration;
C, refining: the 2-HACC bullion after the above-mentioned vacuum-drying is water-soluble, filter, filtrating post precipitation in solvent, whiz obtain refining 2-HACC.
2. the preparation method of 2-HACC according to claim 1; It is characterized in that: the detailed process of the deacetylated processing of chitosan described in the steps A is: chitosan is joined in the strong base solution; In temperature is 110 ℃～120 ℃; Pressure is stirring reaction 5～15 hours under 0.2Mpa～0.4Mpa condition, obtains deacetylation and be 85%～95% chitosan.
3. the preparation method of 2-HACC according to claim 1 and 2 is characterized in that: the solvent described in the steps A is a kind of in Virahol, methyl alcohol, the acetone.
4. the preparation method of 2-HACC according to claim 1 is characterized in that: the mass ratio of chitosan described in the step B and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is 1: 3～7; Whenever dripped a 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride at a distance from 2 hours, divide to drip off for 3 times, the dropping time was controlled at 20～30 minutes at every turn.
5. according to the preparation method of claim 1 or 3 described 2-HACCs, it is characterized in that: the temperature of the heterogeneous reaction described in the step B is for being 80 ℃～85 ℃, and the reaction times is 10-14 hour.
6. according to the preparation method of claim 1 or 3 described 2-HACCs, it is characterized in that: the solvent of separating out 2-HACC bullion among the step B is a kind of in Virahol, methyl alcohol, acetone and the absolute ethyl alcohol.
7. according to the preparation method of claim 1 or 3 described 2-HACCs, it is characterized in that: vacuum drying temperature is 50 ℃～70 ℃ among the step B.
8. the preparation method of 2-HACC according to claim 1 is characterized in that: adopt the 3G sand core funnel to filter among the step C.
9. according to the preparation method of claim 1 or 8 described 2-HACCs, it is characterized in that: the solvent described in the step C is a kind of in Virahol, methyl alcohol, acetone and the absolute ethyl alcohol.
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